FR2484442A1 - PROCESS FOR THE PREPARATION OF MOLYBDENE CONTAINING COMPOSITIONS USEFUL FOR BETTER ECONOMY OF THE FUEL OF INTERNAL COMBUSTION ENGINES - Google Patents

Abstract

PROCESS FOR PREPARING COMPOSITIONS CONTAINING USEFUL MOLYBDENE FOR BETTER ECONOMY OF THE FUEL OF INTERNAL COMBUSTION ENGINES. THE PROCESS OF THE INVENTION IS CHARACTERIZED IN THAT THE FOLLOWING IS REACTED: A. AN ACID CONTAINING PHOSPHORUS REPRESENTED BY THE FORMULA (CF DRAWING IN BOPI) IN WHICH X AND X ARE EACH INDEPENDENT OF OXYGEN OR SULFUR, EACH N IS ZERO OR 1 AND THE RS ARE IDENTICAL OR DIFFERENT HYDROCARBON-BASED RADICALS; B. AT LEAST ONE COMPOUND BASED ON MOLYBDENE HEXAVALENT OXIDE AND C. HYDROGEN SULPHIDE IN THE PRESENCE OF D. A POLAR SOLVENT.

Description

The present invention relates to compositions

  containing sulfur, phosphorus and molybdenum prepared from phosphorus-containing acids. It also relates to compositions containing sulfur, phosphorus and molybdenum having reduced sulfur activity. More particularly, the invention relates to processes for preparing such compositions containing sulfur, phosphorus and molybdenum, which are useful as additives

  in lubricants. In addition, the present invention

  concentrates of these compositions and composi-

  Lubricating compositions comprising these compositions. It also relates to a method for reducing consumption

  of fuel by lubricating an internal combustion engine

  do with these lubricating compositions.

  Sulfurized molybdenum salts of phosphorus-containing acids and processes for preparing such compositions have been described in US Patents. NO 3 223 625,

  3,256,184, 3,400,140, 3,494,866, 3,840,463 and 4,156,099.

  These U.S. patents are incorporated here by reference

  for their descriptions about it.

  A main object of the present invention is to provide novel compositions containing sulfur,

  phosphorus and molybdenum prepared from

  phosphorus and processes for prepa-

rer.

  Another object is to provide novel compositions containing sulfur, phosphorus and molybdenum having reduced sulfur activity prepared from these acids.

containing phosphorus.

  Another goal is to provide new

  positions containing sulfur, phosphorus and molybdenum

  prepared from phosphorus-containing acids which

  feel properties of friction reduction in lubricants. An additional object is to provide new concentrates comprising these sulfur-containing compositions,

2 2484442

phosphorus and molybdenum.

  Another additional goal is to provide new

  lubricating compositions containing these news

  compositions containing sulfur, phosphorus and

  lybdenum reducing friction. Another goal is to provide a new process to reduce fuel consumption by lubricant

  an internal combustion engine with these new components

  containing sulfur, phosphorus and molybdenum

reducing friction.

  These and other goals of the invention are achieved through

  this to a process for the preparation of a composition

  in that an olefinically non-reactive compound is reacted

  saturated able to react with active sulfur with a com-

  position prepared by a process according to which

  gir: (a) a phosphorus-containing acid represented by the formula x R (X ') n X l

P-XH

R (X ') n

  wherein X and X 'are, each independently, oxy-

  gene or sulfur, each n is zero or one and the R's are identical or different hydrocarbon-based radicals; (b) at least one compound based on hexavalent molybdenum oxide and (c) hydrogen sulfide

  in the presence of (d) a polar solvent.

  Typical examples of phosphorus-containing acids (a) from which the compositions according to the present invention can be prepared are known. Illustrative examples of preferred acids containing phosphorus and sulfur are: 1. Dihydrocarbylphosphinodothioic acids, such as amylphosphinodithioic acid, corresponding to the formula

(C5H1 1) S

C-SH;

(C5H11)

  2. S-hydrocarbyl hydrogen-hydrocarbyl phosphonotrithioates, such as S-amyl hydrogen amylphosphonotrithioate, corresponding to the formula

(C5H11)

P-SH;

  (C5H11) -Sf. 3. Hydrogen hydrocarbyl phosphonodithioates

  0-Hydro-carbyl, such as hydrogen-amylphosphonodithioa-

  0-amyl ester, corresponding to the formula

(C5H11 S

(C11-OO-SH;

(C5H11)

  4. S, S-dihydrogenphosphorotetrathioates

  drocarbyl, such as hydrogen phosphate phosphorotetrathioate

myle, corresponding to the formula

(C5H11) S

S / P-SH;

S

(C5H11)

  5. Hydrogen phosphorotrithioates of O, S-dihydro

  such as O, S-hydrogen phosphorotrithioate

  diamyl, corresponding to the formula (CsH11) S (C HS

SH;

(C5Hll)

  6. Hydrogen phosphorodithioates of 0,0-dihydro

  such as hydrogen phosphorodithioate of 0.0-

  diamyle, corresponding to the formula)

-SH;

4 (C H11) /

  Preferred acids of the formula r (Ro) 2PSH 7

  can be easily obtained by the reaction of

  phosphorus sulphide (P2S5) and an alcohol or phenol.

  For the reaction, 4 moles of the alcohol or phenol are mixed with one mole of phosphorus pentasulfide at a temperature of about C to about 200 ° C. Hydrogen

  sulphide is released in this reaction. We prepare

  denies the oxygenated analogues of these acids by treating the dithiolic acid with water or water vapor, which

  in fact replaces one or both of the sulfur atoms.

  Thus, as mentioned above, the preferred phosphorus-containing acids are acids containing

  phosphorus and sulfur. These preferred acids include

  particularly preferably those of the above formula wherein at least one X is sulfur, especially those in which both X's are sulfur; at least one X 'is oxygen or sulfur,

  in particular the two X 'are oxygen and n is 1.

  Mixtures of acids may be used according to

this invention.

  The terminology "hydrocarbon-based radical"

  as used herein ("here" encompassing the claims

  annexed) is used to define a monovalent radical

  substantially saturated hydrocarbon derived by removing

  hydrogen to a carbon atom of the hydrocarbon

  Bure. This carbon atom is directly connected to the

  te of the molecule. These hydrocarbon-based radicals are derived from aliphatic hydrocarbons, hydrocarbons

  cycloaliphatic hydrocarbons, aromatic hydrocarbons, hydro-

  aliphatic-cycloaliphatic mixed carbons, hydro-

  mixed aliphatic-aromatic carbides and mixed cycloaliphatic-aromatic hydrocarbons. As a result, these hydrocarbon-based radicals will be referred to as aliphatic-based radicals, cyclo-aliphatic-based radicals, and the like.

  The basic hydrocarbons from which these radicals are derived

  may contain certain polar or non-polar substituents

  non-reactive or substantially non-reactive hydrocarbons.

  The terminology "substantially saturated" as used

  here must be understood as defining radi-

  substantially free from acetylenic unsaturation

  (-C C-) in which there is no more than one

  thylenic (-C = C-) for 10 (preferably 20)

  carbon-carbon covalent sounds. The so-called "dou-

  bonds in the aromatic nucleus (for example ben-

  zene) should not be considered as contributing to the unsaturation about the terminology "substantially

  saturated. "Usually, there will not be more than one

  yenne of an ethylenic bond per monovalent radical

  Sibly saturated as described above. Preferably (to

  with the exception of aromatic nuclei) all car linkages

  carbon-carbon in a substantially saturated radical will be saturated bonds; that is to say that the radical will be exempt

  acetylenic and ethylenic bonds.

  In general, the hydrocarbon-based radical may contain up to about 30 carbon atoms, it preferably contains from 1 to about 20 carbon atoms. The hydrocarbon-based radicals may contain certain non-reactive or substantially non-reactive polar or non-hydrocarbyl substituents which do not significantly interfere with the reactions or the present compositions, as will be apparent from the present invention.

  well understood by those skilled in the art. Examples represent

  Examples of polar or non-hydrocarbyl substituents are halo substituents, such as chloro, fluoro, bromo and

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  ioda; nitro; lower alkoxy, such as butoxy and hexyloxy; (lower alcohol) thio, such as pentylthio and heptylthio; hydroxy; mercapto;

O O

  CO-hydrocarbyl, for example -C-lower alkyl; o hydrocarbyl-O-chlorocarbyl, etc. As a rule, and

  especially when the compositions according to the present invention

  must be used as lubricating additives

  the degree of substitution and the nature of the substitution

  The hydrocarbon-based radicals are such that the predominantly hydrocarbon character of the radical is not destroyed. Thus, in view of this requirement, these radicals normally have no more than four substituents per radical, and usually no more than one substituent per 10 carbon atoms in the radical. Preferably, the hydrocarbon-based radical is a radical purely

  hydrocarbyl (i.e. a hydrocarbon radical

  holding only carbon and hydrogen atoms).

  The term "inferior!" when it is used here to denote radicals such as lower alkyl radicals must be understood as describing a radical

  containing up to seven carbon atoms.

  Advantageous compositions according to the present

  The invention includes those formed from

  phosphorus in which each R is a hydrocarbyl radical, in particular, independently, a radical

  alkyl, aryl, alkaryl or arylalkyl having up to

  30 carbon atoms, preferably from 3 to about 20

  carbon atoms. Preferred R groups are groups

  Alkyl and alkaryl, preferably alkyl.

  Compounds (b) based on molybdenum oxide

  Hexavalent elements useful for the present invention are

  based on hexavalent molybdenum oxide soluble in water which are acidic under aqueous conditions. The chemistry of the compounds based on hexavalent molybdenum oxide in aqueous solution is well known to those skilled in the art and

  a more complete description is not necessary.

  These acidic compounds of molybdenum hexavalent

  can be obtained from water

  poses containing molybdenum trioxide or mixtures of two or more of these compounds. These molybdenum trioxide-containing compounds include molybdenum trioxide (MoO3) and compounds that are formed from molybdenum trioxide. Compounds containing molybdenum trioxide include

  MoO3, molybdenum trioxide hydrates,

  lybdic acid, ammonium molybdate, molybdates of alkali metals (for example sodium or potassium) and molybdates of heteropolyacids (for example phosphomolybdic acid). The preferred water-soluble acidic compounds based on hexavalent molybdenum oxide are

  molybdenum; molybdic acid; heteropoly molybdates

  acids, especially phosphomolybdates; those produced

  by acidification of molybdates of alkali metals or amines

  monium with, for example, hydrochloric acid, acetic acid or sulfuric acid; and those produced in an aqueous solution of MoO3 or its hydrates, the water solubility of MoO3 or its hydrates having been improved

  by the addition of an acid or a base.

  Also useful as (b) oxyhalogens

  of molybdenum hexavalent such as MoOC14, MoO2C12,

  MoO2Br2, Mo203C16, MoOF4 and mixtures thereof which can be

  be hydrolysed with water to give the acidic compounds

  soluble in water based on hexavalent molybdenum oxide.

  A more detailed discussion of the nature of compounds containing molybdenum trioxide, in particular

  concerning the description, the preparation, the acidity and the

  solubility in water of these compounds, can be found in Molybdenum Compounds, Their Chemistry and Tecbnology, by D. H. Killeffer and A. Linz, Interscience Publishers, New York, 1952, Chapters 4, 6, 7 and 8; and by F.A. Cotton

8 2484442

  and G. Wilkinson, Advanced Inorganic Chemistry, A Comprehen-

  sive Text, 2nd Edition, Interscience Publisher - Depends

  John Wiley and Sons, New York, London, Sidney, 1966, pages 930960, which are incorporated herein by

  reference for their descriptions in this regard.

  Normally, the hexavalent molybdenum compound (b) or its precursor is dispersed or dissolved in a polar solvent (d). Alternatively, (a) and (b) or their progenitors can be combined first and then (d) added. In some cases, it may be advantageous

  to produce (a) and / or (b) in situ, preferably in pre-

  the presence of (d). In the case of (a), for example, a metal salt of the phosphorus-containing acid (eg, an alkali metal salt) could be acidified in the presence of (b) to give (a). In the case of (b), for example, a compound containing molybdenum trioxide can be used to produce a water-soluble acidic compound

  hexavalent molybdenum by acidifying a molybdate of

  alkaline solution in the presence of (a) and (d) to produce (b)

in situ.

  For the purposes of the present invention, it is necessary that a reaction mixture of (a) and (b) be prepared first, preferably in the presence of (d), before

  reaction with hydrogen sulfide (c).

  Hydrogen sulfide (c) is available in

  trade and can be introduced into the reaction chamber

  above or below the surface of the mixture of

  reaction of (a) and (b) in the presence of (d).

  Another source may be H2S produced in situ. For example, alkali metal sulfides, for example

  Na2S, could be acidified with HCl to

  H2S in the presence of (a), (b) and (d).

  The polar solvent (d) useful in the present

  invention comprises water, organic polar solvents

  such as alcohols, ethers, ketones and their mixtures. Preferred polar solvents (d) are -9

  water and mixtures of water and one or more other

  organic polar bears. Organic polar solvents

  preferred are lower alkyl alcohols,

ethers and ketones.

  5. In addition to the polar solvents, the reaction may be conducted in the presence of a substantially inert solvent / liquid diluent medium. This solvent / diluent medium is advantageously used to maintain the contact of the reactants and to facilitate the adjustment of the temperatures of the

  reaction. Examples of solvent / diluent media used are

  readable are aliphatic and aromatic hydrocarbons such as benzene, toluene, naphtha, mineral oil,

  hexane; chlorinated hydrocarbons such as dichlorobenzene

zene and heptyl chloride.

  As used in the description and references

  annexed claims, the phrase "substantially inert", when used in connection with solvents / diluents and similar materials, shall be understood to mean that the solvent / diluent, etc., is sufficiently inert to chemical or physical modifications under the conditions in which it is used not to interfere significantly in an unfavorable way in the preparation, storage,

  the mixing operation and / or the action of the compositions, ad-

  ditives, concentrates, etc., according to the present invention in

  the context of their intended use. For example,

  Many amounts of a solvent / diluent, etc., can undergo minimal reaction or degradation without impeding the implementation and use of the invention as described herein. In other words, such a reaction or degradation, although technically discernible, would not be sufficient to deter a user with normal experience in

  this technique to implement the invention and the

  use for its intended purposes. Thus, the expression "sensi-

  "inert", as used here, will easily be

  taken and appreciated by those skilled in the art.

  As used in this description and

  the appended claims, the expression "medium of

  "diluent" should be understood as encompassing

  Solvent / diluent sites in which each of the reactants independently is soluble or stably dispersible. The expression "dispersibly so

  as used in the description and the recom-

  annexed claims must be understood as meaning

  that a composition (for example a single compound, a

  lange of two or more compounds, etc.) may be dispersed in a given medium to an extent that allows it to act

  in the manner provided. So, for example, when a com-

  position is prepared by an oil reaction, it is sufficient that the reactants can be suspended in the oil in a manner sufficient to

  allow the reaction to occur and that the composi-

  be formed. Thus, the term "solvent / diluent medium" is understood and can be used in a

classic by the skilled person.

  The product of the reactants (a), (b) and (c) in the presence of (d) can be used as a lubricant additive; however, it is preferred that (d) be

  eliminated, especially when (d) is water. The com

  positions prepared by reacting (a), (b) and (c) in the presence of (d) may sometimes be accompanied by the formation of by-products and / or solvent medium /

  excess diluent which may reduce their commercial interest.

  As a result, the polar solvent (d), undesired by-products and / or the excess or undesirable solvent / diluent medium can be separated from the compositions according to

  the present invention by techniques known to the man

  of the art, for example by filtration, evaporation (by

  example stripping), etc., to give a more advanced product

  geous. Alternatively, if the solvent / diluent medium is,

  for example, a base oil that can be used in

  lubricant compositions according to the present invention, the

  can be left in the solvent / diluent medium and used to form the lubricant compositions as

described below.

  Another aspect which in some cases could diminish the commercial interest of the compositions prepared by reacting (a), (b) and (c) in the presence of (d) is the very active sulfur contained in these compositions. This

  sulfur of high activity is usually referred to as

  corrosive or active. This active sulfur is very reactive

  and is corrosive to metals such as copper and silver. Accordingly, a reduction in the active sulfur content of a composition will result in the composition being less corrosive to metals. Active sulfur is well known to those skilled in the art and is not

  no need to talk more about it.

  Sulfur activity contained in the compositions prepared by reacting (a), (b) and (c) in the presence of

  (d) can be deduced by reacting these compositions a-

  with one or more olefinically unsaturated compounds of

  to react with active sulfur.

  The olefinically unsaturated compounds which

  with the very active sulfur contained in the composi-

  prepared by reacting (a), (b) and (c) with

  that of (d) are very diverse in nature. They contain at least one olefinic double bond, which is defined as a nonaromatic double bond; that is, connecting two aliphatic carbon atoms. In its broadest sense, the olefin may be defined by the formula R1R2C = CR3R4, wherein R1, R2, R3 and R4 are each hydrogen or

  an organic radical. In geféral, the groups R in the

  mule above which are not hydrogen may be groups such as -C (R% 3, -COOR5, -CON (R% 2, -COON (R5) 4,

-COOM, -CN,

  NR5 -C, R, -X, -YR or -Ar, each R5, independently, is hydrogen or

  an alkyl, alkenyl, aryl or substituted alkyl group,

1 1

12 2484442

  substituted phenyl or substituted aryl, provided that

  any two R5 groups may be an alkyl group

  alkylene or substituted alkylene so that a ring having up to about 12 carbon atoms is formed; M is an equivalent of a metal cation (preferably Group I or II, for example sodium, potassium, barium or calcium); X is a halogen (for example chlorine, bromine or iodine); Y is oxygen or divalent sulfur;

* Ar is an aryl or substituted aryl radical a-

  up to about 12 carbon atoms in the

  STITUTING. Any two of the substituents R 1, R 2, R 3 and R 3 may also together form an alkylene group or

  substituted alkylene; that is, the olefinic compound

may be alicyclic.

  The nature of the substituents in the substituted portions described above are not normally a critical aspect of the invention and any such substituent is

  useful as long as it is compatible or can be made compatible

  with lubricating environments and is not

  under the proposed reaction conditions. Thus, substituted compounds which are unstable to decompose detrimentally under the reaction conditions,

  used are not envisaged. The choice of substitute

  appropriate killing is within the reach of those skilled in the art or

  can be established by routine tests. Typical examples

  Examples of such substituents are any of the above moieties as well as hydroxy, amidine, amino, sulfonyl, sulfinyl, sulfonate, nitro, phosphate, phosphite, alkali metal, mercapto, etc. substituents.

  The olefinically unsaturated compound is usually

  a compound in which each R group which is not hydrogen is, independently, an alkyl, alkenyl or aryl group or (less often) a substituted radical

  corresponding. Monoolefinic and diolefinic compounds

  fin, especially the former, are preferred, and especially terminal monoolefinic hydrocarbons (alpha-olefins); that is, the compounds wherein R 3 and R 4 are hydrogen and R 1 and R 2 are alkyl or aryl, especially alkyl (i.e.

  the olefin is aliphatic). Olefinic compounds a-

  from about 8 to about 36 and especially about

  8 to about 20 carbon atoms are particularly

vantageux.

  The alpha-olefin (i.e. the final olefin)

  nal) C8_36 aliphatic is usually an olefin

  which is not branched on the olefinic carbon atoms

  c; that is to say which contains the portion CH2 = CH-. Of

  Moreover, it generally does not contain substantially

  cation on allylic carbon atoms; that is, preferably it contains the portion CH2 = CHCH2-

  The preferred olefins are those included in the

  C8-20. Mixtures of these olefins are commercially available and such mixtures are useful in

the present invention.

  In addition, esters of fatty acids derived from

  or more unsaturated carboxylic acids are particularly

  primarily useful as olefinically unsaturated compounds.

  The term "fatty acid" as used herein refers to acids that can be obtained by hydrolysis of a naturally occurring vegetable or animal fat or oil. They are usually in the C16-20 range and include oleic acid, linoleic acid, etc. The fatty acid esters which are used are mainly esters of aliphatic alcohols, including monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, butanols, etc., and

  polyhydric alcohols including ethylene glycol,

  pylene glycol, trimethylene glycol, neopentyl glycol, glycerol, etc. Oils are particularly preferred

2484442-

  fat derived mainly from unsaturated acids, that is,

  that is, naturally occurring triglycerides of long-chain unsaturated carboxylic acids, especially

  linoleic and oleic acids. These fatty oils

  take naturally occurring animal and vegetable oils such as lard oil, peanut oil, cottonseed oil, soybean oil, corn oil, etc. The composition and nature of the fatty oils are well known to those skilled in the art and more detailed information about them is given by M.P. Doss in Properties of the Principal, FATS, Fatty Oils, Waxes,

  Fatty Acids and Their Salts, The Texas Company, 1952,

  document which is incorporated here by reference for its

  description of fatty oils and carboxylic acids

  unsaturated materials useful for the present invention.

  A reaction mixture of (a) and (b) must

  edge be prepared before reaction with (c) in the presence of (d). It is preferred that (d) be present when preparing

  the reaction mixture (a) and (b); and he is especially

  It is preferred to disperse or dissolve (b) in (d) prior to contact with (a). This reaction mixture can be conveniently prepared in a temperature range of

  from about 0 ° C. to about 1500 ° C., preferably about 250 ° C.

around 1000C.

  The reaction of (a), (b) and (c) in the presence of (d) can conveniently be conducted in the temperature range of from 0 to about 1500C. Although it is not

  necessary, it is preferred to adjust the temperature of the

  that it is reasonably constant throughout the course of the reaction. It is particularly preferred to set the temperature in the range of about 500C to

About 1000C.

  The reaction of the compositions prepared by reacting (a), (b) and (c) in the presence of (d) with the olefinically unsaturated compounds capable of reacting with the active sulfur can be conveniently conducted in a temperature range of from About 1000C at about 150C,

  preferably from about 1100C to about 1400C.

  The reaction time varies with several factors including the nature and amount of the reactants, the reaction equipment, the solvent / diluent medium, the degree of agitation, and the like. For the purposes of the present invention, the molecular weight of a phosphorus-containing acid (a) is equal to its equivalent weight, and therefore one mole of (a) is equal to its equivalent weight, which is determined substituting its "acid value" in the following relation: Equivalent weight = 56 100 milligrams of KOH / equivalents acid number (milligrams of KOH / gr)

  The "acid number" is defined as the number of milligrams

  of KOH used to bring the pH of 1 gram

  sample under aqueous conditions at about 4.0. The pH of about 4.0 can be determined by using an indicator that changes color in the range of 3.0

  at 4.5, such as bromophenol blue or by electro-

as with a pH meter. -

  For the purposes of the present invention, the report

  between the reactants (a) and (b) should be from about 0.5 to about 4 moles of the phosphorus-containing acid (a) per mole of molybdenum in (b) (for example, one mole of NaeoO4 contains a molybdenum molde;

  mole of ammonium paramolybdate, (NH4) 6Mo7O2.4H2O,

  seven moles of molybdenum). A report of at least

  about 0.5 moles of hydrogen sulfide per mole of molybdenum

  in the reaction mixture of (a) and (b) is

table.

  Accordingly, ratios (a) :( b) :( c) range from about 0.5 to about 4 moles of (a) for one mole of molybdenum in (b) for at least 0.5 moles of H 2 S. Ratios of about 1: 1: 1.5 are optimal, although excess hydrogen sulfide can be used

  (ie 1: 1: 1.5) to ensure a complete reaction

  you. Ratios of 1: 1: 4 or more can be used, but ratios of 1: 1: 2 must be sufficient for

  ensure a complete reaction. We can eliminate the hydro-

  excess sulphide gene by infusing into the mixture of

  reaction an inert gas such as nitrogen.

  The preferred amount of olefinically unsaturated compound useful for the purposes of the present invention is the minimum amount required for reaction with all the active sulfur present in the prepared composition.

  by reacting (a), (b) and (c) in the presence of (d).

  It is believed that for each 1.5 mol of hydrogen sulfide (c) used per mol of molybdenum in (b), 0.5 mol of active sulfur is produced in the reaction of (a), (b) and (c) in the presence

  of (d). In addition, an olefinic double bond is

  to react with two moles of active sulfur.

  As a result, the minimum amount of olefinically saturated compound required is based on the stoichiometric relationship of an olefinic double bond for two

  moles of active sulfur produced. Although this report

  the reaction stoichiometrically, more

  larger or smaller olefinically unsaturated compounds

  can be used as required.

  For example, we will normally use larger quantities

  tures (stoichiometric excesses) of the olefinically unsaturated compound to increase the rate of reaction and

  a complete reaction of the active sulfur.

  The secondary solvent (d) is essentially a

  engine or a contact agent. As a result, the minimum amount of polar solvent (d) is the amount needed

  for the reaction of (a), (b) and (c) to occur (ie

  that is, hydrogen sulfide reacts with (a) and (b) in the presence of (d). Generally, we use enough

  (d) to disperse or, preferably, dissolve the compounds

  containing molybdenum trioxide or the molybdenum oxyhalide compounds previously described. Usually from about 1 to about 4 parts of (d) will be used for each part by weight of the molybdenum compound

  described above used. Quantities of (d) very

  than those indicated above would not be

  abnormal, but would not be beneficial.

  The present invention is illustrated by the following examples. Obviously, these examples should not be considered as limiting the invention, because a modification of the examples by ordinary expedients

  will be readily apparent to those skilled in the art.

  In all examples, unless otherwise specified, all temperatures are in 0C, all parts are parts by weight and all percentages

are derived from parts by weight.

Example 1

  A reaction mixture is prepared by adding

  from 2035 parts (9.17 moles) of P2S5 to 7335 parts (36.68 moles) of a commercially available C12 alcohol 14

  801C under a nitrogen atmosphere. P2S5 is added in one

  two-hour period and the release of heat from the

  reaction brings the temperature to 950C during the ad-

  edition. The hydrogen sulfide formed as a result of the reaction is removed continuously and captured by a

  caustic soda solution. The mixture is allowed to cool

  reaction while shaking it for two hours under

  nitrogen. The reaction mixture is filtered to obtain the

  O, O-di-C12-14 phosphorodithiolecide which has a

96 acid dice.

Example 2

  The procedure of Example 1 is repeated, except that the C12-14 alcohol is replaced on an equimolar basis by 2-ethylhexyl alcohol to give the desired O, O-di-2-ethylhexyl phosphorodithioic acid. who

has an acid number of 137.

Example 3

  A reaction mixture is prepared by adding

  a mixture of 584 parts (1 mole) of the 0.0-di-

  C12-14 phosphorodithioic prepared in Example 1 and 500 parts of toluene to a solution at room temperature (260C) of 40 parts (1 mole) of sodium hydroxide, 190 parts of water and 144 parts (1 mole ) of

  molybdenum trioxide prepared by heating up to

  a clear solution. Once the addition is complete

  After this reaction, 100 parts (1 equivalent) of concentrated hydrochloric acid are added to the reaction mixture. We are heating

  the reaction mixture at 400C for two hours.

  Hydrogen sulfide (90 parts, 2.6 moles) was added to the reaction mixture by addition below the surface over a period of three hours. During

  the addition of hydrogen sulphide, the temperature of the

  the reaction mixture is brought to 90.degree.

  The reaction mixture is then flushed with excess hydrogen sulfide by nitrogen blowing, subjected to vacuum stripping, and filtered to obtain the desired sulfur, phosphorus and molybdenum-containing composition formed from the nitrogen. 'acid

0.0-di-C12-14 phosphorodithioic acid.

Example 4

  A reaction mixture is prepared by adding

  of 3,275 parts (8 moles) of the acid 0,0-di-2-ethyl-

  hexylphosphorodithioic acid prepared in Example 2 to a slurry at room temperature of 1,152 parts (8.0

  moles) of molybdenum trioxide in 2000 parts of water.

  The reaction mixture is heated to 800 ° C. and 533 parts of hydrogen sulfide are added by addition below the surface over a period of 6.5 hours. We maintain the

  reaction mixture at 80-901C during the addition of

  hydrogen sulphide. The reaction mixture is then purged with excess hydrogen sulfide by nitrogen blowing and subjected to stripping at 95 ° -100 ° C.

19 2484442

  to obtain as a residue the desired composition containing sulfur, phosphorus and molybdenum formed from an O, O-di-2-ethylhexylphosphorodithiolic acid

Example 5

  An aqueous solution of phosphomolybdic acid is prepared by heating 360 parts (2.5 moles) of molybdenum trioxide, 24 parts of 85% phosphoric acid and 2000 parts of water to boiling for three hours.

  hours, then filtering the mixture through. paper-

  filter and washing the residue with 150 parts of water. We

  reduces the total volume of the resulting solution of

  to obtain 921 parts of solution containing 19.37%

of molybdenum.

Example 6

  A reaction mixture is prepared by adding

  dropwise drop of 1475 parts (3.0 moles) of

  phosphomolybdic acid prepared in Example 5 to 1228

  parts (3 moles) of 0,0-di-2-ethylhexylphosphoric acid

  rodithioic prepared in Example 2 at room temperature.

  in a period of 1 hour. The reaction mixture is then maintained at 55 ° C. for 3.5 hours. The reaction mixture was refluxed while blowing hydrogen sulfide below the surface. We keep

  the reaction mixture at 90-95 C for three hours

  continue to inject hydrogen sulphide

  Furé. A total of 242 parts of hydrogen is thus added

  sulphurized to the reaction mixture. We then purge the

  reaction mixture of hydrogen sulphide in excess by

  nitrogen sufflation. Toluene (1000 parts) is added to the reaction mixture and water is removed by azeotropic distillation. The reaction mixture is filtered and then stripped from toluene by stripping at 95 ° C. under vacuum to obtain the desired composition containing sulfur, phosphorus and molybdenum formed from an acid.

  0,0-di-2-éthylhexylphosphorodithioique.

Example 7

  A reaction mixture is prepared by adding

  a mixture of 2050 parts (5.0 moles) of the 0.0-di-

  2-ethylhexylphosphorodithioic prepared in Example 2

  and 2,500 parts of toluene to a solution at room temperature

  room temperature prepared by heating 200 parts (5 moles) of sodium hydroxide, 1000 parts of water and 720

  parts (5.0 moles) of molybdenum trioxide to

  a clear solution and then adding 39

  parts (0.25 mole) of 85% phosphoric acid to the

  lution. After the addition is complete, 500

  (5 moles) concentrated hydrochloric acid to the reaction mixture and then the reaction mixture is heated

  at 40WC for two hours. Hydrogen sulphate is added

  fired to the reaction mixture (318 parts, 9.35 moles) by addition below the surface in a period of ten

  hours. During the addition of hydrogen sulphide, the temperature

  The temperature of the reaction mixture is raised to reflux temperature. The reaction mixture is then purged of excess hydrogen sulfide by nitrogen blowing and subjected to vacuum stripping at 90 ° C. Toluene (2000 parts) is added to the reaction mixture which is

  filter and then subjected to stripping to obtain

  hold the desired composition containing sulfur, phosphorus

  phore and molybdenum formed from a 0.0-di-

2-éthylhexylphosphorodithio! That.

Example 8

  A reaction mixture of 1152 parts (8 moles) of molybdenum trioxide, 77 parts (0.67 moles) of acid

  85% phosphoric acid, 3,000 parts water and 3,275 parts

  (8 moles) of 0,0-di-2-ethylhexylphosphorodithiol

  that prepared in Example 2 is heated to 850C. 533 parts of hydrogen sulfide are added by addition to the reaction mixture below the surface over a period of 6.5 hours. The reaction mixture is maintained at 80-90 ° C during the addition of the hydrogen sulfide. The reaction mixture is then purged of excess hydrogen sulfide by

21 2484442

  nitrogen blowing and subjected to stripping at

  -1000C under vacuum to obtain as residue the composition

  desired content containing sulfur, phosphorus and

  libdene formed from an O, O-di-2-ethylhexyl acid

phosphorodithiolque.

Example 9

  A reaction mixture of 4557 parts of the

  composition containing sulfur, phosphorus and

  lybdenum prepared in Example 4 and 1137 parts of a commercially available mixture of alpha-olefins in

  C15 18 is heated at 11301C for three hours. We are

  be the reaction mixture to obtain the desired product.

Example 10

  The procedure of Example 9 is repeated, except that the C1518 alpha-olefin is replaced by a mixture of 1139 parts of a commercially available soybean oil and 681 parts of a mixture. available

  in the trade of C15 alpha-olefins 18.

Example 11

  The procedure of Example 10 is repeated, except that the sulfur-containing composition is replaced,

  phosphorus and molybdenum, by equal weight, by the

  containing molybdenum prepared in Example 6.

Example 12

  A reaction mixture of 446 parts of the

  position containing sulfur, phosphorus and molybdenum

  prepared in Example 3, 73 parts of soybean oil

  commercially available and 34 parts of a mixture

  available in the trade of alpha-olefins in C15-18 is

  heated at 125-135oC for six hours. We dilute the mixture

  reaction with 2,500 parts of toluene and filtered

  be. The filtrate is stripped to obtain the

desired product.

  As indicated above, the compositions

  The present invention is also useful as an additive

  for lubricants, in which they act principally

2484442-

  as oxidation inhibitors, anti-wear agents

  and / or extreme pressure agents and friction modifiers

  ment. They can be used in various lubricants to

  basis of various oils with a lubricating viscosity, com-

  taking natural and synthetic lubricating oils and mixtures thereof. These lubricants include oils

  for internal combustion engines with

  spark ignition and compression ignition engines, including automobile and truck engines, two-stroke engines, air piston engines, marine and rail diesel engines, etc. We can use them

  also in gas engines, generating sets

  xes and turbines, etc. Fluids for transmissions

  tomatoes, lubricants for combined rear axle gearbox assembly, gear lubricants,

  lubricants for metal working, hydraulic fluids

  and other lubricating oil and grease compositions may also be improved by incorporation.

  compositions according to the present invention.

  Natural oils include animal oils

  vegetable oils (eg castor oil, lard oil) as well as liquid petroleum oils and acid-treated or solvent-treated mineral lubricating oils of the paraffinic, naphthenic or

  mixed paraffinic-naphthenic. Oils of a viscosity

  Lubricants derived from coal and shale are also

  if useful base oils. Synchronous lubricating oils

  theories include hydrocarbon oils and oils

  halogenated hydrocarbons such as homopoly olefins

  for example, polybutenes, polypropylenes, propylene-isobutylene copolymers,

  chlorinated polybutylenes, poly (1-hexenes), poly (l-

  octenes), poly-1-decenes), etc., and mixtures thereof; alkylbenzenes (for example dodecylbenzenes,

  tetradecylbenzenes, dinonylbenzenes, di- (2-ethyl-

  hexyl) benzenes, etc.); polyphenyls (eg, biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl oxides and alkylated diphenyl sulfides and their derivatives, analogs and homologs, etc .; Homopolymers and interpolymers of alkylene oxides and their derivatives in which the terminal hydroxyl groups have been modified by esterification,

  Etherification, etc., constitute another class of oil.

  known synthetic lubricants. Examples in

  are the oils prepared by polymerization of

* ethylene or propylene oxide, alkyl ethers

  and aryls of these polyoxyalkylene polymers (e.g.

  polyisorpopylene glycol methyl ether having an average molecular weight of 1000, polyethylene glycol diphenyl ether having a molecular weight of 500 to 1000, polypropylene glycol diethyl ether having

  a molecular weight of 1000 to 1500, etc.) or their

  mono- and polycarboxylic, for example esters

  of acetic acid, esters of C3-C8 fatty acids,

  Jangé or Oxo acid diester in C13 of tetraethylene-

glycol.

  Another appropriate class of lubricating oils

  Synthetics include the dicarboxylic acid esters

  (for example phthalic acid, succinic acid,

  alkyl succinic acids, alkenyl succinic acids,

  maleic acid, azelaic acid, sulfuric acid,

  sebacic acid, fumaric acid, adipic acid and

  that, of the dimer of linoleic acid, acids alkyl malo-

  alkenyl malonic acids, etc.) with various alcohols (eg butyl alcohol, hexyl alcohol,

  dodecyl alcohol, 2-ethylhexyl alcohol, ethylene-gly-

  col, diethylene glycol monoether, propylene glycol, etc.).

  Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, fumarate

  of di-n-hexyl, dioctyl sebacate, di-alkyl azela-

  isooctyl, diisodecyl azela late, dioctyl phthalate

248444442

  tyl, didecyl phthalate, dieicosyl sebacate, -: 2-ethylhexyl diester of linoleic acid dimer,

  the complex ester formed by reacting one mole of acid

  linoleic acid, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like. Esters useful as synthetic oils

  also include those formed from mono-

  C5 to C12 boxyl and polyols and polyol ethers

  neopentyl glycol, trimethylolpropane, penta

  erythritol, dipenta-erythritol, tripenta-erythritol, etc.

  Silicon-based oils such as polyal-

  alkyl, polyaryl, polyalkoxy or polyaryloxy siloxanes and

  silicate oils constitute another class which is

  synthetic lubricants (eg tetraethyl silicate, tetraisopropyl silicate, silicate

  of tetra (2-ethylhexyl), tetra (4-methyl-2) silicate

  ethylhexyl), tetra- (p-tert-butylphenyl) silicate,

  hexa- (4-methyl-2-pentoxy) -disiloxane, poly (methyl) -

  siloxanes, poly (methylphenyl) siloxanes, and :.). other

  synthetic lubricating oils include esters -

  phosphorus-containing acid liquids (eg phos-

  tricresyl phate, trioctyl phosphate, digester ester,

  phosphonic acid, etc.), tetrahydro-

polymeric furans, etc.

  Unrefined, refined and rereffi-

  (and their mutual mixtures) of the type described above.

  may be used in lubricating compositions.

  in accordance with the present invention. Non-fresh oils

  Finished are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retort distillation operations, a petroleum oil obtained directly from distillation or an ester oil obtained directly from an esterification process and used without

  other treatment would be an unrefined oil. The oil

  the refined ones are similar to unrefined oils, except that they have been further processed in one or more purification steps to improve one or more properties. Many such techniques of

  purification are known to those skilled in the art, as the former

  solvent traction, acid or basic extraction, filtration, Wercolation, etc. Refinished oils are obtained by processes similar to those used to obtain refined oils applied to oils

  refined that have already been used in service. These oils

  rerffinates are also called regenerated or re-treated oils and often are further processed by techniques for the removal of used additives and

  of decomposition products of the oil.

  Generally, lubricants according to the present

  the invention contain a quantity of the composition

  the present invention sufficient to give it a

  better oxidation stability and / or better

  anti-wear and / or extreme pressure and / or

  duction of friction. Normally, this amount will be from about 0.05% to about 20%, preferably about 0.1%

  about 100%, in particular up to about 5% and

  from about 0.5% to about 2% of the total weight of

  brifiant. In lubricating oils used under extremely unfavorable conditions, such as lubricating oils for marine Siesel engines, the reaction products according to the present invention may be present.

  in proportions of up to about 30% by weight.

  The invention also contemplates the use of other

  additives in combination with the compositions according to

  this invention. These additives include, for example, ash-type or ash-producing auxiliary detergents and dispersants, corrosion inhibitors and the like.

  oxidation, pour point depressants,

  extreme pressure, the stabilization agents of the

color and antifoaming agents.

  Examples of detergents producing

  dre are neutral and basic salts soluble in the oil of alkali or alkaline earth metals with acids

  sulphonic acids, carboxylic acids or organic acids

  phosphorus-containing compounds characterized by at least one direct carbon-phosphorus linkage such as those prepared by treating an olefin polymer (eg polyisobutene having a molecular weight of 1000) with a phosphorising agent such as trichloride phosphorus,

  phosphorus heptasulfide, phosphonium pentasulphide

  re, phosphorus trichloride and sulfur, phosphorus

  and a sulfur halide or phosphoric chloride

  thioîque. The most commonly used salts of these

  are those of sodium, potassium, lithium, calcium

  cium, magnesium, strontium and barium.

  The expression "basic salt" is used to describe

  sign metal salts in which the metal is present

  in quantities stoichiometrically larger than the radi-

  organic acid callus. Commonly used processes for preparing basic salts include heating a

  solution in the mineral oil of an acid with a stoe excess

  of a metal neutralizing agent such as metal oxide, hydroxide, carbonate, bicarbonate or sulfide at a temperature above 50WC and filtration of the resulting mass. The use of a "promoter" in the neutralization step to assist in the incorporation of a large excess of metal is also known. Examples of compounds useful as a promoter

  phenolic substances such as phenol

  naphthol, an alkyl phenol, thiophenol, an alkyl

  sulphurised phenol and formaldehyde condensation products

  hyde with a phenolic substance; alcohols such as

  ethanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol and

27 2484442

  cyclohexyl alcohol; and amines such as aniline,

  phenylenediamine, phenothiazine, phenylbeta;

  naphthylamine and dodecylamine. A particular process

  The most effective method for preparing the basic salts comprises mixing an acid with an excess of a basic neutralizing agent derived from an alkaline earth metal and

  at least one alcohol promoter, and carbonation of the mem-

  at a high temperature such as 60 to 2000C.

  The ashless auxiliary detergents and dispersants are so called despite the fact that, according to its constitution, the dispersant can give by combustion a non-volatile material such as boric oxide or

  phosphoric anhydride; however, it does not usually contain

  usually not metal and therefore does not burn ash containing a metal. Many types are known in the art and any of them

  can be used in lubricants according to this

  vention. Examples are:

  (1) Reaction products of carboxylic acids

  (Or derivatives thereof) containing at least about 34 and preferably at least about 54 carbon atoms with

  compounds containing 1 nitrogen such as an amine,

  hydroxylated organic compounds such as phenols and alcohols.

  cools and / or basic inorganic materials. Examples

  These "carboxylic dispersants" are described in

  British Patent No. 1,306,529 and in many

  United States vets including the following:

3,163,603 3,351,552 3,541,012

3,184,474 3,381,022 3,542,678

3,215,707 3,399,141 3,542,680

3 219 666 3 415 750 3 567 637

3 271 310 3 433 744 3574 101

3,272,746 3,444,170 3,576,743

3 281 357 3 448 048 3 630 904

3,306,908 3,448,049 3,632,510

3 311 558 3 451 933 3 632 5i1

3,316,177 3,454,607 3,697,428

3,340,281 3,467,668 3,725,441

3,341,542 3,501,405 Re 26,433

3,346,493 3,522,179

  (2) Reaction products of aliphatic or alicyclic halides of relatively

  with amines, preferably polyalkylene

  lyamines. They can be characterized as "amine dispersants" and examples are described, for example, in the following U.S. patents:

3,275,554 3,454,555

3 438 757 3 565 804

  (3) Alkylphenol reaction products in

  which the alkyl group contains at least about 30

  volumes of carbon with aldehydes (especially formaldehyde

  dehyde) and amines (especially polyalkylenes)

  lyamines), which can be characterized as "Mannich dispersants". The materials described in U.S. Patents. Examples are:

3413 347 3 725 480

3,697,574 3,726,882

3,725,277

  (4) Products obtained by submitting the

  carboxylic persists, amine or Mannich to further treatment with reagents such as urea, thiourea,

  carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbyl succinic anhydrides,

  nitriles, epoxides, boron compounds,

  phosphorus, etc. Examples of such materials are described in U.S. patents. following:

  3036 003 3 282 955 3 493 520 3 639 242

  3087 936 3 312 619 3 502 677 3 649 229

  3200 107 3366 569 - 3 513 093 3 649 659

  3216 936 3 367 943 3 533 945 3 658 836

3254025 3 373111 3539633 3697574

  3256 185 3 403 102 3 573 010 3 702 757

29 2484442

  3 278 550 3 442 808 3 579 450 3 703 536

  3,280,234 3,455,831 3,591,598 3,704,308

  3,281,428 3,455,832 3,600,372 3,708,522

  (5) Interpolymers of monomers having a solubilizing effect in oil such as methacrylate

  decyle, vinyl and decyl oxide and

  of high polecular weight with monomers containing

  polar substituents, for example acrylates

  aminoalkyl or acrylamides and acrylates with

  Poly (oxyethylene) compounds can be characterized as "polymeric dispersants" and examples are described in the following U.S. Patents:

3,329,658 3,666,730

3,449,250 3,687,849

3519565 3702300

  The patents cited above are incorporated here

  by reference for their descriptions of dispersants without

ash.

  Examples of extreme pressure agents and

  Inhibitors of corrosion and oxidation are hy-

  chlorinated aliphatic hydrocarbons such as chlorinated paraffin; organic sulfides and polysulfides such as benzyl disulfide, bis (chlorobenzyl) disulfide,

  dibutyl tetrasulfide, the methyl sulfide ester of a-

  oleic acid, a sulphurated alkyl phenol, dipentene sulphide and terpene sulphide; phosphosulfurized hydrocarbons as the reaction product of a phosphorus sulphide with

  turpentine or methyl oleate; phosphate esters

  phore comprising mainly dihydrophosphite phosphites

  carbyl and trihydrocarbyl such as dibut phosphite

  tyl, diheptyl phosphite, dicyclo

  hexyl, pentylphenyl phosphite, diphosphite

  pentylphenyl, tridecyl phosphite, distearyl phosphite, dimethyl and naphthyl phosphite, oleyl and pentylphenyl phosphite, polypropylene phosphite (molecular weight 500) phenyl, diisobutyl-phenyl phosphite; metal thiocarbamates as

  zinc dioctyldithiocarbamate and heptylphenyl dithio-

  barium carbamate; phosphorodithioates of Group II metals such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, di (heptyl)

  phenyl) -phosphorodithioate of barium, dinonylphospno-

  cadmium rodithioate and the zinc salt of a phos-

  phorodithiol produced by the reaction of pentasulfide

  of phosphorus with an equimolar mixture of isopropyl alcohol

pylyl and n-hexyl alcohol.

  The compositions according to the present invention may

  can be added directly to the lubricant. Preferably

  however, they are diluted with a standard organic diluent

  substantially inert liquid such as a mineral oil.

  naphtha, benzene, toluene or xylene to form an additive concentrate. These concentrates contain

  usually about 20 to 90% by weight of the composition.

  according to the invention and may contain, in addition, one or more other additives known in the art or

described above.

  Lubricating compositions prepared according to

  the present invention can be illustrated by a

  lubricating position prepared by treating a mineral oil

  of lubricating viscosity with 1% by weight of

example of example 9.

Claims (19)

  1) A process for preparing a composition,   characterized in that (a) a phosphorus-containing acid represented by the formula is reacted. R (X ') n X n -XH R (X ') '11   wherein X and X 'are each independently of the oxy-   gene or sulfur, each n is zero or 1 and the R's are identical or different hydrocarbon-based radicals;   (b) at least one molyb oxide compound   hexavalent diene and (c) hydrogen sulphide   in the presence of (d) a polar solvent.   2) A process according to claim 1, characterized in that the hydrocarbon-based radical is an aliphatic-based radical and contains up to about 30 atoms of carbon.   3) A method according to claim 2, characterized   in that the aliphatic-based radical is a radical al-   and contains from about 3 to about 30 carbon atoms.   4) A process according to claim 3, characterized in that at least one X is sulfur; at least one X 'is oxygen; and each n is 1.   A process according to claim 4, characterized in that a reaction mixture of (a) and (b) is first prepared in the presence of (d), which is then reacted.   with (c) at a temperature of 0 to 1500C.   6) A method according to claim 5, characterized   in that (d) consists of water, organic solvents, or mixtures thereof.   7) A process according to claim 1, characterized in that the hexavalent molybdenum oxide compound is a water-soluble hexavalent acid molybdenum compound which is obtained from molybdenum trioxide compounds or mixtures of one or more of these compounds. 8) A process according to claim 7, characterized in that the compounds based on molybdenum trioxide are   molybdenum trioxide, molybdenum trioxide hydrate,   molybdic acid, ammonium molybdates,   alkali metal lybdates or molybdates of heteropoly   lyacides. 9) A method according to claim 4, characterized in that the copipose (b) based on hexavalent molybdenum oxide   is a water-soluble acidic compound of molybdenum hexava-   slow that is obtained from trioxide-based compounds   molybdenum or mixtures of one or more of these compounds.   A process according to claim 9, characterized in that the molybdenum trioxide compounds are molybdenum trioxide, molybdenum trioxide hydrate,   molybdic acid, ammonium molybdates, molybdates   alkali metals or molybdates of heteropolyaides.   11) A method according to claim 6, characterized in that the hexavalent molybdenum oxide compound (b) is a hexavalent molybdenum molybdenum water-soluble compound which is obtained from trioxide-based compounds.   molybdenum or mixtures of one or more of these compounds.   12) A method according to claim 11, characterized in that the compounds based on molybdenum trioxide are molybdenum trioxide, molybdenum trioxide hydrate, molybic acid, ammonium molybdates, molybdates   alkali metals or molybdates of heteropolyacids.   13) A method according to claim 8, characterized in   what the molybdates of heteropolyacids are the phospho-   molybdates. A process according to claim 10, characterized -3-5 14)   in that the molybdates of heteropolyacids are phos-   phomolybdates. A process according to the claim in that the molybdates of heteropolyacids * 5 phomolybdates.   16) A process according to claim in that (d) is water.   17) A process according to claim in that (d) is water.   18) A process according to claim in that (d) is water.   19) A process according to claim in that (d) is water.   ) A process according to claim in that (d) is water.   21) A process according to claim in that (d) is water.   22) A process according to claim in that (d) is water. 12, characterized are the phos-   1, characterized 4, characterized 6, characterized 8, characterized, characterized 12, characterized, characterized 23) A composition prepared by the process according to claim 24) A composition prepared by a process according to   one of claims 4, 6, 10, 16, 17, 18 or 22.   ) A lubricating composition comprising a   majority of an oil with a lubricating viscosity and a   minor amount of at least one composition according to the sales 23.   26) A lubricating composition comprising a quantity   major part of an oil with a lubricating viscosity and a   minor amount of at least one composition according to the 24.   27) An additive concentrate comprising from 20 to 90% of at least one composition according to claim 23 and a   normally liquid organic diluent, substantially inert.   28) An additive concentrate comprising from 20 to 90% of at least one composition according to claim 24 and a   normally liquid organic diluent, substantially inert.   29) A method for reducing the fuel consumption of an internal combustion engine, characterized in that the engine is greased in use with the composition   lubricant according to claim 25.   ) A process for reducing the consumption of   of an internal combustion engine, characterized in that the engine is greased in use with a composition   lubricant according to claim 26.